Fused [1,2,4]oxadiazolylidenebenzenesulfonamides and their use as herbicides and plant growth regulants

ABSTRACT

Fused [1,2,4]oxadiazolylidenebenzenesulfonamides such as 2-chloro-N-(5,7-dimethyl-2H-[1,2,4]oxadiazolo-[2,3-a]pyrimidin-2-ylidene)benzenesulfonamide and 2-chloro-N-(7-methoxy-5-methyl-2H-[1,2,4]oxadiazolo-[2,3-a][1,3,5]triazin-2-ylidene)benzenesulfonamide are general and selective pre- or post-emergence herbicides and can be useful in regulating plant growth.

RELATED APPLICATION

This application is a continuation-in-part of my copending applicationU.S. Ser. No. 228,705, filed Jan. 26, 1981, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novel fused[1,2,4]oxadiazolylidenebenzenesulfonamides and to their use as generaland selective pre- or post-emergence herbicides and as plant growthregulants.

U.S. Pat. No. 3,154,548 discloses compounds of the formula: ##STR1##where

R is alkyl, halo- and aryl-substituted alkyl, aryl and halo-, nitro-,and alkyl-substituted aryl; and

R¹ is alkyl, hydroxy- and arayl-substituted alkyl, aryl and halo-,nitro- and alkyl-substituted aryl. The compounds are described aschelating agents.

B. Bobranski et al., in Arch. Immunol. Theor. Exp., 16 (5), 804 (1968)disclose the compound: ##STR2## No utility was disclosed in theabstract.

R. Gompper et al. in Chem. Ber., 99, 2900 (1966) discloses compounds ofthe formula: ##STR3## where

R is CH₃, C₆ H₅, p--Cl--C₆ H₄ and p--CH₃ --C₆ H₄. These compounds aretaught to be intermediates.

M. Hamana et al. in Chem. Pharm. Bull., 22 (7), 1506-1518 (1974)disclose the compound: ##STR4## No utility is taught.

SUMMARY OF THE INVENTION

The present invention relates to novel compounds of Formula I, tocompositions containing them and to their use as general and selectivepre- or post-emergence herbicides and as plant growth regulants.##STR5## where

R is C₁ -C₄ alkyl, C₁ -C₁ alkoxy, F, Cl, Br, NO₂, COR₄, SO₂ R₅, SO₂ NR₆R₇, SO₂ OCH₂ CF₃, SO₂ OCH₂ CCl₃, SO₂ N(OCH₃)(CH₃), BR₈, OSO₂ R₉ or CH₂P;

R₁ is H, F, Cl, Br, CF₃, NO₂, C₁ -C₄ alkyl or C₁ -C₄ alkoxy;

R₄ is C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₂ -C₆ haloalkoxy substitutedwith 1-3 atoms selected from F, Cl, or Br, C₅ -C₆ cycloalkoxy, --O(CH₂CH₂ O)_(n) R₁₀ or OCH₂ CH₂ CH₂ OR₁₀ ;

n is 1 or 2;

R₅ is C₁ -C₄ alkyl;

R₆ and R₇ are independently C₁ -C₄ alkyl, provided the total number ofcarbon toms of R₆ and R₇ does not exceed 5;

B is O or SO₂ ;

R₈ is CHF₂, CF₃, CH₂ CF₃, CF₂ CHFG where G is F, Cl, Br or CF₃ ;

R₉ is C₁ -C₄ alkyl or C₁ -C₄ alkyl substituted with 1-3 atoms selectedfrom F, Cl or Br;

P is C₁ -C₄ alkoxy, C₃ -C₄ alkenyloxy or SO₂ R₅ ;

R₁₀ is CH₃ or CH₃ CH₂ ; X is CH₃, CH₃ CH₂, CH₃ O or CH₃ CH₂ O;

Y is H, Cl, CF₃, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, CH₂ OCH₃, CH₂ OCH₂ CH₃,CH₂ CH₂ OCH₃ or CH₂ CH₂ OCH₂ CH₃ ; and

Z is CH or N.

Preferred in order of increasing activity and/or increasingly favorableease of synthesis are those compounds of Formula I wherein:

(1)

R is C₁ -C₄ alkyl, C₁ -C₄ alkoxy, F, Cl, Br, CF₃, SO₂ R₅, BR₈, OSO₂ R₉or CH₂ P, where P is C₁ -C₄ alkoxy; and

R₁ is H, F, Cl, Br, CF₃, C₁ -C₄ alkyl or C₁ -C₄ alkoxy.

(2) Compounds of preferred (1) wherein R₁ is H.

(3) Compounds of preferred (2) wherein

R is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, F, Cl, Br, CF₃, SO₂ R₅, BR₈, OSO₂ R₉or CH₂ P;

provided that:

(a) when R is SO₂ R₅, then R₅ is C₁ -C₃ alkyl;

(b) when R is BR₈, then BR₈ is SO₂ CF₃ or OCF₂ CF₂ H;

(c) when R is OSO₂ R₉, then R₉ is C₁ -C₃ alkyl or CF₃ ; and

(d) when R is CH₂ P, then P is CH₃ O.

(4) Compounds of preferred (3) wherein

Y is H, CF₃, C₁ -C₂ alkyl, C₁ -C₂ alkoxy or CH₂ OCH₃.

(5) Compounds of preferred (4) wherein

X is CH₃ or CH₃ O; and Y is CH₃ or CH₃ O.

Specifically preferred for high activity and/or ease of synthesis arethe following compounds of Formula I:

2-Chloro-N-(5,7-dimethyl-2H-[1,2,4]oxadiazolo[2,3-a]pyrimidin-2-ylidene)benzenesulfonamide;

2-Chloro-N-(5-methoxy-7-methyl-2H-[1,2,4]oxadiazolo[2,3-a]pyrimidin-2-ylidene)benzenesulfonamide;

2-Chloro-N-(7-methoxy-5-methyl-2H-[1,2,4]oxadiazolo[2,3-a][1,3,5]triazin-2-ylidene)benzenesulfonamide;and

2-Chloro-N-(7-methoxy-5-methyl-2H-[1,2,4]oxadiazolo[2,3-a][1,3,5]triazin-2-ylidene)benzenesulfonamide.

This invention also relates to novel compounds of Formula II which arevaluable intermediates for the preparation of herbicides of thisinvention. ##STR6## wherein

X, Y and Z are as previously defined.

Preferred Intermediates, in order of increasingly favorable ease ofsynthesis and/or high activity of the herbicides of Formula I, arecompounds of Formula II wherein:

(1) Y is H, CF₃, C₁ -C₂ alkyl, C₁ -C₂ alkoxy or CH₂ OCH₃.

(2) Compounds of preferred (1) wherein X is CH₃ or CH₃ O, and Y is CH₃or CH₃ O.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

Many of the compounds of Formula I can be prepared by reacting anaminoheterocyclic-N-oxide of Formula III with an N-(substitutedphenylsulfonyl)carbonimidic dichloride of Formula IV as shown inEquation 2. Compounds of Formula IV can be prepared fromdimethyl-N-(substituted phenylsulfonyl)carbonimidodithioates of FormulaV by treatment with a chlorinating agent such as sulfuryl chloride, asshown in Equation 1. ##STR7## wherein

R, R₁, X, Y and Z are as previously defined.

The reaction of Equation 1 is best carried out in an inert aproticorganic solvent such as methylene chloride or chloroform at ambientpressure and temperature. The mode of addition is not critical; however,it is often convenient to add the sulfuryl chloride to a solution of thecompound of Formula V. Since the sulfuryl chloride is a liquid, itsaddition can be easily controlled.

The product of Formula IV can be isolated by concentration of thereaction mixture under reduced pressure, and it may be used in thesubsequent step without intermediate purification.

The reaction of Equation 2 is best carried out in an inert aproticorganic solvent such as tetrahydrofuran or ethylene glycol dimethylether, at ambient pressure and temperature. It is often convenient tofirst mix the reactants III and IV in an inert solvent and then addsodium hydride in portions to this mixture. The desired product isisolated by evaporation of solvents, addition of the concentratedreaction mixture to water and filtration. The product can be purified bywashing with ether.

Alternatively, compounds of Formula I may also be prepared by reactingan appropriately substituted benzenesulfonyl chloride of Formula VI withan 1,2,4-oxadiazlo[2,3-a]heterocyclicimine hydrobromide of Formula II,as shown in Equation 3: ##STR8##

R, R₁, X, Y and Z are as previously defined.

The reaction of Equation 3 may best be carried out in inert aproticorganic solvents such as methylene chloride or tetrahydrofuran at atemperature in the range of about -20° C. to 10° C. Two equivalents of abase such as trimethylamine, triethylamine, DABCO or sodium hydride maybe used. It is often convenient to mix VI and II in an inert solventfirst and then add base in portions to this mixture.

The desired product of Formula I may be isolated by filtration andconcentration of the filtrate. The crude product may be further purifiedby column chromatography.

A. Carbonimidodithioate Intermediates

Many of the intermediate dimethyl N-(substitutedphenylsulfonyl)carbonimidodithioates of Formula V can be prepared bytreatment of corresponding arylsulfonamides with carbon disulfide andpotassium hydroxide followed by reaction of the dipotassium salt withmethyl iodide as shown in Equation 4. ##STR9## wherein

R and R₁ are as previously defined except in those instances where R isCOR₄ or NO₂.

The arylsulfonamide is dissolved in dimethylformamide (DMF) with anequivalent amount of carbon disulfide and two equivalents of potassiumhydroxide are added in portions at ambient pressure and temperature. Themixture is stirred for 1-8 hours and methyl iodide is then added to thestirred suspension at ambient pressure and temperature. The mixture isthen stirred for another 2-6 hours. The dimethyl N-(substitutedphenylsulfonyl)carbonimidodithioate which is formed can be isolated byaddition of the reaction mixture to water and filtration. The productcan be purified by washing with a solvent such as ether or hexane.

The preparation of sulfonamides from ammonium hydroxide and sulfonylchloride is widely reported in the literature, e.g., Crossley et al., J.Am. Chem. Soc., 60, 2223 (1938).

Certain sulfonyl chlorides are best prepared by chlorosulfonation of asubstituted benzene in carbon tetrachloride according to the teaching ofH. T. Clarke et al., Org. Synth. Coll. Vol. 1, 2nd Ed., 1941, p. 85.Other benzenesulfonyl chlorides are best made by diazotization of theappropriate aniline with sodium nitrite in HCl, followed by reaction ofthe diazonium salt with sulfur dioxide and cuprous chloride in aceticacid according to the teaching of H. L. Yale and F. Sowinski, J. Org.Chem. 25, 1824 (1960).

Many of the intermediate dimethyl N-(substitutedphenylsulfonyl)carbonimidodithioates of Formula V may also be preparedby reacting an appropriately substituted arylsulfonamide withtri(methylthio)methyl tetrafluoroborate as shown in Equation 5.##STR10## wherein

R and R₁ are as previously defined.

The reaction of Equation 5 may best be carried out in inert aproticorganic solvents such as methylene chloride or chloroform at 0° C. to60° C.

The dimethyl N-(substituted phenylsulfonyl)carbonimiodoithioate ofFormula V may be isolated by evaporation of the solvent, trituration ofthe residue with water and filtration. The product may be purified bywashing with a solvent such as ether or hexane.

Tri(methylthio)methyl tetrafluoroborate can be prepared from dimethylcarbonotrithioate and trimethyloxonium fluoroborate according to theprocedure taught by W. P. Tucker and G. L. Roof in Tetrahedron Lett.,2747 (1967).

The method used for preparing the intermediate sulfonamides when R isSO₂ NR₆ R₇ is included in Equations 6a-d. ##STR11## wherein

R₁, R₆ and R₇ are as previously defined.

In step (6a), the o-nitrobenzenesulfonyl chlorides in Formula a, whichare well-known in the art, are treated with an amine, R₆ R₇ NH, in aninert organic solvent such as methylene chloride, ethyl ether, ortetrahydrofuran at 0°-50° C. The amine may be taken in excess to act asan acid acceptor; alternatively, a tertiary amine such as triethylamineor pyridine may be used as an acid acceptor. The by-product aminehydrochloride is filtered off or washed out of the solvent with waterand the product isolated by evaporation of the solvent.

The reduction described in step (6b) is accomplished by treating asolution of the compounds of Formula b in a solvent such as ethanol,ethyl acetate, or DMF, in a pressure vessel with 100-1000 pounds persquare inch of hydrogen at 80°-150° C. in the presence of ahydrogenation catalyst such as 5-10% palladium absorbed on carbon. Whenthe theoretical amount of hydrogen has been absorbed, the solution iscooled and the catalyst is removed by filtration. The product is thenisolated by evaporation of the solvent.

The diazotization and coupling with sulfur dioxide, described in step(6c) is accomplished in the following manner. A solution of thesulfamoyl compound of Formula c in a mixture of concentratedhydrochloric acid and glacial acetic acid is treated with a solution ofsodium nitrite in water at -5° to 0° C. After stirring for 10-15 minutesat 0° C. to insure complete diazotization, this solution is added to amixture of an excess of sulfur dioxide and a catalytic amount of cuprouschloride in glacial acetic acid at 0°-5° C. The temperature is kept at0°-5° C. for 1/4 to 1 hour and is then raised to 20°-25° C. and held atthat temperature for 2-4 hours. This solution is then poured into alarge excess of ice-water. The sulfonyl chloride products, d, can beisolated by filtration or by extraction into solvent such as ethyl etheror methylene chloride followed by evaporation of the solvent.

The amination described in step (6d) is conveniently carried out bytreating a solution of the sulfonyl chloride of Formula d with an excessof anhydrous ammonia in a solvent such as ethyl ether or methylenechloride at 0°-25° C. If the product sulfonamide is insoluble it may beisolated by filtration followed by washing out the salts with water. Ifthe product sulfonamide is soluble in the reaction solution, it may beisolated by filtering off the precipitated ammonium chloride andevaporating the solvent.

The sulfonamide precursors to intermediates of Formula IV in which R isSO₂ OCH₂ CF₃, SO₂ OCH₂ CCl₃ or SO₂ N(CH₃)OCH₃ can be prepared through asequence analogous to that shown in Equations 6a-d. In step 6a, theamine is replaced by the appropriate alkoxide salt orN-methoxy-N-methylamine and the resulting nitro compound is treated asin Equations 6b-d.

Equation 7 describes the preparation of intermediate sulfonamides ofFormula VIII when R is SO₂ R₅. ##STR12## wherein

R₁ and R₅ are as previously defined.

The thioether of Equation 7a may be prepared from the appropriate2-aminothiophenol and an alkyl halide as described in the literature,e.g., R. N. Prasad et al., Can. J. Chem. 44, 1247 (1966). The formationof the sulfonamide c is analogous to that presented in Equations 6c and6d above.

The oxidation of c to the corresponding2-alkylsulfonylbenzenesulfonamides of Equation 7c may be carried oututilizing any of several of standard literature procedures withm-chloroperbenzoic acid (C. R. Johnson, et al., Tetradedron, 25, 5649(1969)), or with aqueous hydrogen peroxide in acetic acid (F. G.Bordwell, et al., J. Amer. Chem. Soc. 77, 1141, (1955).

The intermediate sulfonyl chlorides and the sulfonamides VIII in which Ris CH₂ P (wherein P is as previously defined) may be synthesized fromthe corresponding nitrobenzenes by reduction, then diazotization in thepresence of sulfur dioxide and cuprous chloride as shown above.

The o-alkoxymethyl- or o-alkylsulfonylmethylnitrobenzenes are in turnprepared via "Williamson Synthesis", according to Equations 8a or 8b.##STR13## "Williamson Synthesis" has been widely used for thepreparation of ethers as reviewed by W. Theilheimer, Syn. Methods ofOrg. Chem., Vol. VII, p. 112. The thioethers formed in Equations 8a or b(W=S) may then be oxidized to the corresponding sulfones in a mannersimilar to that described in Equation 7c.

Benzenesulfonamides of Formula X can also be derived from compound IX asillustrated in Equation 8c. ##STR14##

Preparation of o-sulfamylbenzoic acid esters, IX, from saccharin orsulfobenzoic acid anhydride is well-known in the art, e.g., B. Loev andM. Kormendy, J. Org. Chem. 27, 1703 (1962). The esters, IX, can bereadily reduced to the ethers, X, with diborane in a suitable organicsolvent, e.g., tetrahydrofuran, in the presence of fifteen fold excessof boron trifluoride etherate under reflux for 18 hours, as described byR. P. Graber and M. B. Meyers, J. Org. Chem. 26, 4773 (1961).

The compounds of this invention in which R is an ortho sulfonatederivative (OSO₂ R₉) may also be prepared via the correspondingsulfonamides of Formula VIII. These intermediates may be prepared asdescribed in "Research Disclosure", p. 52, (1978).

B. Aminoheterocyclic-N-Oxide Intermediates

The aminoheterocyclic-N-oxides of Formula III can be prepared as shownbelow in Equation 9 by the reaction of an appropriately substitutedaminoheterocycle XI with an oxidizing agent such asm-chloroperoxybenzoic acid. ##STR15## wherein

X, Y and Z are as previously defined.

As shown in Equation 9, an aminoheterocycle is reacted with an oxidizingagent such as m-chloroperoxybenzoic acid in aprotic solvent such asacetone, methylethylketone, methylene chloride or chloroform.Temperatures of 20°-80° C. over 2-15 hours are usually required tocomplete the reaction. The products are isolated by cooling andfiltration. Alternatively, if the aminoheterocyclic-N-oxides III aresoluble in the solvents chosen, they may be isolated by stirring thereaction mixture with potassium carbonate or sodium carbonte, filtrationand concentration of the filtrate. The crude aminoheterocyclic-N-oxidesIII may be purified by washing with solvents such as acetone, ether orethyl acetate. In cases that X and Y are different, there may be twoisomeric compounds of Formula III formed. The two N-oxide isomers may beseparated, for example, by column chromatography and reacted as inEquation 2 or they may be used as a mixture in this reaction to give thecorresponding isomeric mixture of two products which is also useful forpracticing this invention.

The compounds of Formula III may also be prepared from aminoheterocyclesXIII by the sequence of reactions described in Equation 10. ##STR16##wherein

Y and Z are as previously defined; and

R' is CH₃ or CH₃ CH₂ and T is Cl or Br.

The reaction of Equation 10a is best carried out in an aprotic solventsuch as acetone, methylethylketone, methylene chloride or chloroform.Temperatures of 20°-80° C. over 2-15 hours are usually required tocomplete the reaction. The product XIII are isolated by cooling andfiltration. Alternatively, if the aminoheterocyclic-N-oxides XIII aresoluble in the solvent chosen, they may be isolated by stirring thereaction mixture with potassium carbonate or sodium carbonate,filtration and concentration of the filtrate. The crudeaminoheterocyclic-N-oxides XIII may be purified by washing with solventssuch as acetone, ether or ethyl acetate.

Displacement of the halogen T of compound XIII may be accomplished asshown in Equation 10b by treatment of the aminoheterocyclic-N-oxidesXIII with a solution of an alkali metal alkoxide in the correspondingalcohol, such as sodium methoxide in methanol. Temperatures of 40°-78°C. over 2 to 20 hours are usually required to complete the reaction. Theproduct XIV may be isolated by filtration, acidification of the filtrateand evaporation of the solvent. Purification of the products XIV may beaccomplished by refluxing the crude residue in solvents such as ethylacetate or acetone followed by cooling and collecting the resultingsolid products by filtration.

The synthesis of heterocyclic amines has been reviewed in "The Chemistryof Heterocyclic Compounds", published by Interscience Publ., New Yorkand London. 2-Aminopyrimidines are described by D. J. Brown in Vol. XVIof this series. The 2-amino-1,3,5-triazines are reviewed by K. R.Huffman and in "The Triazines" of this same series. The synthesis oftriazines is also described by F. C. Schaefer, U.S. Pat. No. 3,154,547and by K. R. Huffman and F. C. Schaeffer, J. Org. Chem. 28, 1816 (1963).

C. Fused [1,2,4]oxadiazolo[2,3-a]heterocyclicimine hydrobromideintermediates

Many of the intermediate fused [1,2,4]oxadiazolo[2,3-a]heterocycliciminehydrobromides of Formula II can be prepared by reacting anaminoheterocyclic-N-oxide of Formula III with cyanogen bromide, as shownin Equation 11. ##STR17## wherein

X, Y and Z are as previously defined.

The reaction of Equation 11 is best carried out in protic organicsolvents such as ethanol or methanol at 25°-80° C. over 1-8 hours. Themode of addition is not critical; however, it is often convenient to addcyanogen bromide to a solution of the aminoheterocyclic-N-oxide. Thedesired product is isolated by evaporation of solvents, trituration ofthe residue with a solvent such as methylene chloride or ether andfiltration.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides. Acid addition salts, useful in this invention, can beobtained by reacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The compounds of this invention and their preparation are furtherillustrated by the following examples wherein temperatures are given indegrees centigrade and all parts are by weight unless otherwiseindicated.

EXAMPLE 1 4,6-Dimethyl-1-oxide-2-pyrimidinamine

A solution of 24.0 g of m-chloroperoxybenzoic acid in 200 ml of acetonewas added to a solution of 13.0 g of 4,6-dimethyl-2-pyrimidinamine in300 ml of acetone with stirring. The mixture was stirred at roomtemperature for about two hours. The precipitate was then collected byfiltration, washed with acetone and dried to yield 11.0 g of4,6-dimethyl-1-oxide-2-pyrimidinamine, m.p. 252° C. (dec.).

NMR (DMSO-d₆)δ: 2.2 (s, 3H); 2.3 (s, 3H); 6.7 (s, 1H); 7.53 (b, 2H) ppm.

EXAMPLE 2 4-Chloro-6-methyl-1-oxide-2-pyrimidinamine

A solution of 28.0 g of m-chloroperoxybenzoic acid in 200 ml of acetonewas added to a solution of 17.3 g of 4-chloro-6-methyl-2-pyrimidinaminein 500 ml of acetone with stirring. The mixture was stirred at roomtemperature overnight. The precipitate was then collected by filtration,washed with acetone and dried to yield 13.0 g of4-chloro-2-methyl-1-oxide-2-pyrimidinamine, m.p. 155° C. (dec.).

NMR (DMSO-d₆)δ: 2.35 (s, 3H); 6.95 (s, 1H); 8.06 (b, 2H) ppm.

EXAMPLE 3 4-Methoxy-6-methyl-1-oxide-2-pyrimidinamine

A solution of 11.2 g of 4-chloro-6-methyl-1-oxide-2-pyrimidinamine and5.4 g of sodium methoxide in 200 ml of methanol was refluxed for 12hours. The reaction mixture was then cooled down to room temperature andwas filtered. The filtrate was acidified with concentrated hydrogenchloride solution to pH 7. The filtrate was then evaporated to dryness.The residue was washed with ether, boiling ethyl acetate and then ether.The solid collected was dried to yield 10.0 g of4-methoxy-6-methyl-1-oxide-2-pyrimidinamine, m.p. 199°-201° C.

NMR (TFA)δ: 2.53 (s, 3H); 4.02 (s, 3H); 6.3 (s, 1H); 6.9 (b, 2H) ppm.

EXAMPLE 4 Dimethyl N-(2-chlorophenylsulfonyl)carbonimidodithioate

To a stirred solution of 28.75 g of 2-chlorobenzenesulfonamide in 75 mlof dimethylformamide at ambient temperature was added 8.45 g ofpotassium hydroxide and 4.55 ml of carbon disulfide. The mixture wasstirred at ambient temperature for 2 hours. To this mixture was thenadded another 8.45 g of potassium hydroxide and 4.55 ml of carbondisulfide. The mixture was stirred at ambient temperature for another 2hours and then cooled to about 5° C. To this mixture was added 23.0 g ofmethyl iodide. Another 23 g of methyl iodide was then added at ambienttemperature. The mixture was stirred at ambient temperature for twohours and then added to 1 liter of chilled water. The precipitate wascollected by filtration, and dried to yield 20.0 g of dimethylN-(2-chlorophenylsulfonyl)carbonimidodithioate, m.p. 119°-123° C.

NMR (DMSO-d₆)δ: 2.6 (s, 6H); 7.5-8.4 (m, 4H) ppm.

EXAMPLE 52-Chloro-N-[5,7-dimethyl-2H-[(1,2,4)oxadiazolo(2,3-a)pyrimidin-2-ylidene]benzenesulfonamide

To a dry stirred solution of 2.0 g ofdimethyl-N-(2-chlorophenylsulfonyl)carbonimidodithioate in 10 ml ofmethylene chloride at ambient temperature was added 3.0 g of sulfurylchloride. The resulting mixture was stirred at ambient temperatureovernight and then refluxed for another 3 hours. The mixture was cooleddown to room temperature and 2.0 g of sulfuryl chloride was added. Themixture was stirred at room temperature for an additional 2 days. Thesolvent was evaporated under reduced pressure. To the stirred residueoil was added a suspension of 1.0 g of4,6-dimethyl-1-oxide-2-pyrimidinamine in 30 ml of anhydroustetrahydrofuran. To the above mixture was added 0.54 g of 60% sodiumhydride in portions at ambient temperature. The mixture was stirred atroom temperature for 2 days then concentrated to half of the originalvolume under reduced pressure and added to 250 ml of distilled water.The precipitate was collected by filtration, washed with ether and driedto yield 0.7 g of2-chloro-N-[5,7-dimethyl-2H-[(1,2,4)oxadiazolo(2,3-a)pyrimidin-2-ylidene]]benzenesulfonamide,m.p. 185°-186° C. (dec.).

NMR (DMSO-d₆)δ: 2.5 (d, 6H); 7.2 (s, 1H); 7.3-8.3 (m, 4H) ppm.

EXAMPLE 62-Chloro-N-[5-methoxy-7-methyl-2H-[(1,2,4)oxadiazolo(2,3-a)pyrimidin-2-ylidene]]benzenesulfonamide

To a stirred solution of 2.0 g ofdimethyl-N-(2-chlorophenylsulfonyl)carbonimidodithioate in 10 ml ofanhydrous methylene chloride at ambient temperature was added 4.0 g ofsulfuryl chloride. The mixture was stirred at room temperature for 2days. To this mixture at ambient temperature was added another 1.4 g ofsulfuryl chloride, and the mixture was stirred at room temperature foranother day. The solvent was evaporated under reduced pressure. To thestirred residue oil was added a suspension of 1.1 g of4-methoxy-6-methyl-1-oxide-2-pyrimidinamine in 30 ml of anhydroustetrahydrofuran. To this mixture was added 0.54 g of 60% sodium hydridein portions. The mixture was stirred at room temperature for 2 days thenconcentrated to half of the original volume under reduced pressure andadded to 250 ml of distilled water. The precipitate was collected byfiltration, washed with ether and dried to yield 1.2 g of2-chloro-N-[5-methoxy-7-methyl-2H-[(1,2,4)oxadiazolo(2,3-a)pyrimidin-2-ylidene]]benzenesulfonamide,m.p. 178° C. (dec.).

NMR (DMSO-d₆)δ: 2.53 (s, 3H); 3.97 (s, 3H); 6.8 (s, 1H); 7.3-8.3 (m, 4H)ppm.

EXAMPLE 7 5,7-Dimethyl-2H-[1,2,4]oxadiazolo[2,3-a]pyrimidine-2-iminehydrobromide

To a stirred solution of 14.0 g of 4,6-dimethyl-1-oxide-2-pyrimidinaminein 200 ml of absolute ethanol at ambient temperature and pressure wasadded 16.0 g of cyanogen bromide. The mixture was refluxed for 1 hour.Charcoal was then added, and the mixture was refluxed for another 10minutes and then filtered. The filtrate was concentrated under reducedpressure. The residue oil was triturated with ether followed bymethylene chloride. The solid crystallized was collected by filtration,washed with methylene chloride and dried to yield 12 g of5,7-dimethyl-2H-[2,3,4]oxadiazolo[2,3-a]pyrimidine-2-imine hydrobromide,m.p. 153°-154° C. (dec.).

IR (cm⁻¹): 1700 cm⁻¹.

EXAMPLE 82-Nitro-N-[5,7-dimethyl-2H-[(1,2,4)oxadiazolo(2,3-a)pyrimidin-2-ylidene]]benzenesulfonamide

To a stirred suspension of 1.6 g of5,7-dimethyl-2H-[1,2,4]oxadiazolo[2,3-a]pyrimidine-2-imine hydrobromideand 1.4 g of o-nitrobenzenesulfonyl chloride in 60 ml of anhydrousmethylene chloride at 0° C. is added a solution of 1.0 g oftriethylamine in 10 ml of anhydrous methylene chloride dropwise. Afteraddition, the mixture is stirred at 0° C. for 0.5 hour and then atambient temperature for 2.5 hours. The mixture is then filtered. Thefiltrate is concentrated under reduced pressure and then columnchromatographied (silica gel) to yield2-nitro-N-[5,7-dimethyl-2H-[1,2,4)oxadiazolo(2,3-a)pyrimidin-2-ylidene]]benzenesulfonamide.

EXAMPLE 9 Dimethyl,N-[[2-[(Dimethylamino)sulfonyl]phenyl]sulfonyl]carbonimidodithioate

To a dry stirred solution of 0.9 g ofN,N-dimethyl-1,2-benzenedisulfonamide in 25 ml of acetonitrile atambient temperature was added 2.0 g oftri(methylthio)-methyltetrafluoroborate and then 0.9 g of 2,6-lutidine.This mixture was heated at 60° C. for 3 days. The mixture was cooleddown to room temperature and was evaporated under reduced pressure todryness. The residue was then column chromatographed [silica gel, ethylacetate/methylene chloride (1/10)] to yield 1.08 g of dimethyl,N-[[2-[(dimethylamino)sulfonyl]phenyl]sulfonyl]carbonimidodithioate,m.p. 150°-153° C.

NMR (DMSO-d₆)δ: 2.53 (s, 6H); 2.8 (s, 6H); 7.6-8.46 (m, 4H).

EXAMPLE 10N,N-Dimethyl-N'-(5,7-dimethyl-2H-1,2,4-oxadiazolo[2,3-A]-pyrimidin-2-ylidene)-1,2-benzenedisulfonamide

To a dry stirred solution of 1.8 g of dimethyl,N-[[2-[(dimethylamino)sulfonyl]phenyl]sulfonyl]carbonimidodithioate in10 ml of methylene chloride at ambient temperature was added 4 g ofsulfuryl chloride. This mixture was stirred at room temperature for 2days. To this solution is then added 1 ml of additional sulfurylchloride. The mixture was stirred at ambient temperature for anadditional 24 hours and was then evaporated under reduced pressure. Tothe residue oil was added a dry stirred suspension of 0.75 g of4,6-dimethyl-1-oxide-2-pyrimidinamine in 22 ml of tetrahydrofuran. Tothis stirred mixture at ambient temperature was then added 0.4 g of 60%sodium hydride portionwise. This mixture was then stirred at roomtemperature for 2 days. The mixture was then concentrated to half of itsoriginal volume under reduced pressure and was poured into 200 ml ofice-water. The solid precipitate was filtered, washed with ether anddried in an oven to yield 1.0 g ofN,N-dimethyl-N'-(5,7-dimethyl-2H-1,2,4-oxadiazolo[2,3-A]-pyrimidin-2-ylidene)-1,2-benzenedisulfonamide,m.p. 123°-125° C. (dec.).

NMR (DMSO-d₆)δ: 2.5 (s, 3H); 2.6 (s, 3H); 2.8 (s, 6H); 7.25 (s, 1H);7.66-8.53 (m, 4H).

By application of one or more of the procedures of Examples 1 through 10and/or the general procedures described above, the compounds of Tables Iand II can be prepared.

                                      TABLE Ia                                    __________________________________________________________________________     ##STR18##                                                                    R            R.sub.1 X   Y       m.p. (°C.)                            __________________________________________________________________________    CH.sub.3     H       CH.sub.3                                                                          CH.sub.3                                             C.sub.2 H.sub.5                                                                            H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.3     5-Cl    OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H       OCH.sub.3                                                                         OCH.sub.3                                            CH(CH.sub.3).sub.2                                                                         H       CH.sub.3                                                                          CH.sub.3                                             C(CH.sub.3).sub.2                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             CH.sub.3     5-NO.sub.2                                                                            CH.sub.3                                                                          OCH.sub.3                                            CH.sub.3     5-CH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                            OCH.sub.3    H       CH.sub.3                                                                          CH.sub.3                                             OCH.sub.3    H       CH.sub.3                                                                          OCH.sub.3                                            OC.sub.2 H.sub.5                                                                           H       OCH.sub.3                                                                         CH.sub.3                                             OCH(CH.sub.3).sub.2                                                                        H       OCH.sub.3                                                                         OCH.sub.3                                            OC(CH.sub.3).sub.3                                                                         H       OCH.sub.3                                                                         CH.sub.3                                             OCH(CH.sub.3)C.sub. 2 H.sub.5                                                              3-F     CH.sub.3                                                                          OCH.sub.3                                            OCH.sub.3    6-Br    OCH.sub.3                                                                         OCH.sub.3                                            Cl           H       CH.sub.3                                                                          CH.sub.3                                                                              185-186°                              Cl           H       CH.sub.3                                                                          OCH.sub.3                                                                             178° (dec)                            Cl           H       OCH.sub.3                                                                         CH.sub.3                                             Cl           H       OCH.sub.3                                                                         OCH.sub.3                                            Cl           6-CH.sub.3                                                                            CH.sub.3                                                                          C.sub.2 H.sub.5                                      Cl           H       OCH.sub.3                                                                         CH.sub.2 OC.sub.2 H.sub.5                            Cl           5-NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                     Cl           H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                      80° (d)                               Br           H       CH.sub.3                                                                          CH.sub.3                                             Br           H       OCH.sub.3                                                                         OCH.sub.3                                            F            H       OCH.sub.3                                                                         CH.sub.3                                             F            H       CH.sub.3                                                                          OCH.sub.3                                            CF.sub.3     H       CH.sub.3                                                                          CH.sub.3                                             CF.sub.3     H       OCH.sub.3                                                                         OCH.sub.3                                            CF.sub.3     H       OC.sub.2 H.sub.5                                                                  CH.sub.3                                             CF.sub.3     H       CH.sub.3                                                                          CF.sub.3                                             NO.sub.2     H       CH.sub.3                                                                          H                                                    NO.sub.2     H       CH.sub.3                                                                          OCH.sub.3                                            NO.sub.2     H       OCH.sub.3                                                                         CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                   NO.sub.2     6-Cl    OCH.sub.3                                                                         OCH.sub.3                                            NO.sub.2     H       OC.sub.2 H.sub.5                                                                  CH.sub.2 CH.sub.2 OCH.sub.3                          CO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          H                                                    CO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         O(CH.sub.2).sub.3 CH.sub.3                           CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          OCH(CH.sub.3).sub.2                                  CO.sub.2 C.sub.2 H.sub.5                                                                   H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH(CH.sub.3).sub.2                                                                H       OC.sub.2 H.sub.5                                                                  OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                         H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                       H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 (CH.sub.2).sub.5 CH.sub.3                                                         H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 CH.sub.2 CHCH.sub.2                                                               H       CH.sub.3                                                                          Cl                                                   CO.sub.2 CH.sub.2 CHCH.sub.2                                                               H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.2 CHCHCH.sub.3                                                             H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.4 CHCH.sub.2                                                       H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH.sub.2 CF.sub.3                                                                 H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                              H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 (CH.sub.2).sub.3 Br                                                               H       CH.sub.3                                                                          OCH.sub. 3                                           CO.sub.2 (CH.sub.2).sub.4 CHBrCH.sub.2 Br                                                  H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH(CF.sub.3)CH.sub.3                                                              H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.2 CCl.sub.3                                                                H       CH.sub.3                                                                          Cl                                                    ##STR19##   H       CH.sub.3                                                                          CH.sub.3                                              ##STR20##   H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                       H       CH.sub.3                                                                          H                                                    CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.2 CH.sub.3                                              H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.5                                       H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 (CH.sub.2).sub.3 OCH.sub.3                                                        H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                 H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         CH(CH.sub.3).sub.2                                   SO.sub.2 C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   C.sub. 2 H.sub.5                                     SO.sub.2 CH(CH.sub.3).sub.2                                                                H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                         H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                         H       OCH.sub.3                                                                         OCH.sub.3                                            SO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                       H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 OCH.sub.2 CF.sub.3                                                                H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 OCH.sub.2 CCl.sub.3                                                               H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 N(OCH.sub.3)CH.sub.3                                                              H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                     SO.sub.2 N(CH.sub.3).sub.2                                                                 H       CH.sub.3                                                                          CH.sub.3                                                                              123-125° (dec)                        SO.sub.2 N(CH.sub.3).sub.2                                                                 H       CH.sub.3                                                                          OCH.sub.3                                                                             235-236°                              SO.sub.2 N(CH.sub.3).sub.2                                                                 H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                        H       OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                   SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                          H       OCH.sub.3                                                                         OCH.sub.3                                            SO.sub.2 N(CH.sub.3)(CH.sub.2).sub.3 CH.sub.3                                              H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 N[CH(CH.sub.3).sub.2 ]CH.sub.3                                                    H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                                 H       OCH.sub.3                                                                         (CH.sub.2).sub.3 CH.sub. 3                           OCHF.sub.2   H       OCH.sub.3                                                                         OCH.sub.3                                            OCF.sub.3    H       CH.sub.3                                                                          CH.sub.3                                             OCH.sub.2 CF.sub.3                                                                         H       CH.sub.3                                                                          CF.sub.3                                             OCF.sub.2 CHF.sub.2                                                                        H       CH.sub.3                                                                          Cl                                                   OCF.sub.2 CHFCl                                                                            H       CH.sub.3                                                                          OCH.sub.3                                            OCF.sub.2 CHFBr                                                                            H       OCH.sub.3                                                                         CH.sub.3                                             OCF.sub.2 CHFCF.sub.3                                                                      H       OC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.5                                     SO.sub.2 CHF.sub.2                                                                         H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 CH.sub.2 CF.sub.3                                                                 H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 CF.sub.3                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 CF.sub.2 CHF.sub.2                                                                H       OCH.sub.3                                                                         OCH.sub.3                                            SO.sub.2 CF.sub.2 CHFCF.sub.3                                                              H       CH.sub.3                                                                          CH.sub.3                                             OSO.sub.2 CH.sub.3                                                                         H       CH.sub.3                                                                          OCH.sub.3                                            OSO.sub.2 CH.sub.3                                                                         H       CH.sub.3                                                                          CH.sub.3                                             OSO.sub.2 C.sub.2 H.sub.5                                                                  H       CH.sub.3                                                                          OCH.sub.3                                            OSO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                        H       OCH.sub.3                                                                         CH.sub.3                                             OSO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                        H       OCH.sub.3                                                                         OCH.sub.3                                            OSO.sub.2 CH.sub.2 Cl.sub.2 Cl                                                             H       OCH.sub.3                                                                         CH.sub.3                                             OSO.sub.2 CF.sub.3                                                                         H       CH.sub.3                                                                          CH.sub.3                                             OSO.sub.2 CH.sub.2 CCl.sub.3                                                               H       OCH.sub.3                                                                         H                                                    OSO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Br                                                    H       OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 OCH.sub.3                                                                         H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 OC.sub.2 H.sub.5                                                                  H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.2 O(CH.sub.2).sub.2 CH.sub.3                                                        H       OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 OC(CH.sub.3).sub.3                                                                H       OCH.sub.3                                                                         OCH.sub.3                                            CH.sub.2 OCH(CH.sub.3).sub.2                                                               H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 OCH.sub.3                                                                         3-OCH.sub.3                                                                           OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 OCH.sub.3                                                                         H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                     CH.sub.2 OCH.sub.2 CHCH.sub.2                                                              H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.2 OCH.sub.2 CHCHCH.sub.3                                                            H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 OCH.sub.2 C(CH.sub.3)CH.sub.2                                                     H       OCH.sub.3                                                                         OCH.sub.3                                            CH.sub.2 SO.sub.2 CH.sub.3                                                                 H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                        H       OCH.sub.3                                                                         OCH(CH.sub.3).sub.2                                  CH.sub.2 SO.sub.2 CH.sub.3                                                                 H       CH.sub.3                                                                          O(CH.sub.2).sub.3 CH.sub.3                           CH.sub.2 SO.sub.2 CH(CH.sub.3).sub.2                                                       H       OCH.sub.3                                                                         OCH.sub.3                                            CH.sub.2 SO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.2 SO.sub.2 CH.sub. 3                                                                H       OC.sub.2 H.sub.5                                                                  CH.sub.3                                             CH.sub.2 SO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                H       C.sub.2 H.sub.5                                                                   OCH.sub.3                                            CH.sub.2 OC.sub.2 H.sub.5                                                                  5-OCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                             Cl           5-C.sub.2 H.sub.5                                                                     CH.sub.3                                                                          CH.sub.3                                             CH.sub.3     5-CH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                          OCH.sub.3                                            OCH.sub.3    5-(CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                                                          OCH.sub.3                                            Br           3-O(CH.sub.2).sub.2 CH.sub.3                                                          OCH.sub.3                                                                         OCH.sub.3                                            F            5-CF.sub.3                                                                            OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          5-OC(CH.sub.3).sub.3                                                                  CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          5-NO.sub.2                                                                            CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                                 H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                      108-110° (d)                          __________________________________________________________________________

                  TABLE Ib                                                        ______________________________________                                         ##STR21##                                                                    R           R.sub.1                                                                              X       Y         m.p. (°C.)                        ______________________________________                                        Cl          H      OCH.sub.3                                                                             CH.sub.2 OC.sub.2 H.sub.5                          CF.sub.3    H      CH.sub.3                                                                              CF.sub.3                                           NO.sub.2    H      OCH.sub.3                                                                             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                 NO.sub.2    H      OC.sub.2 H.sub.5                                                                      CH.sub.2 CH.sub.2 OCH.sub.3                        CO.sub.2 CH.sub.3                                                                         H      OCH.sub.3                                                                             O(CH.sub.2).sub.3 CH.sub.3                         CO.sub.2 CH.sub.3                                                                         H      CH.sub.3                                                                              OCH(CH.sub.3).sub.2                                CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                      H      CH.sub.3                                                                              H                                                  SO.sub.2 CH.sub.3                                                                         H      OCH.sub.3                                                                             CH(CH.sub.3).sub.2                                 SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                       H      OCH.sub.3                                                                             CH.sub.2 OCH.sub.3                                 SO.sub.2 N(CH.sub.3).sub.2                                                                H      OCH.sub.3                                                                             (CH.sub.2).sub.3 CH.sub.3                          OCH.sub.2 CF.sub.3                                                                        H      CH.sub.3                                                                              CF.sub.3                                           OSO.sub.2 CH.sub.2 CCl.sub.3                                                              H      OCH.sub.3                                                                             H                                                  CH.sub.2 OCH.sub.3                                                                        H      OCH.sub.3                                                                             OC.sub.2 H.sub.5                                   CH.sub.2 SO.sub.2 CH.sub.3                                                                H      CH.sub.3                                                                              O(CH.sub.2).sub.2 CH.sub.3                         CO.sub.2 CH.sub.3                                                                         H      CH.sub.3                                                                              H                                                  ______________________________________                                    

                                      TABLE IIa                                   __________________________________________________________________________     ##STR22##                                                                    R            R.sub.1 X   Y       m.p. (°C.)                            __________________________________________________________________________    CH.sub.3     H       CH.sub.3                                                                          CH.sub.3                                             C.sub.2 H.sub.5                                                                            H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.3     5-Cl    OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 CH.sub.2 CH.sub.3                                                                 H       OCH.sub.3                                                                         OCH.sub.3                                            CH(CH.sub.3).sub.2                                                                         H       CH.sub.3                                                                          CH.sub.3                                             C(CH.sub.3).sub.2                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             CH.sub.3     5-NO.sub.2                                                                            CH.sub.3                                                                          OCH.sub.3                                            CH.sub.3     5-CH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                            OCH.sub.3    H       CH.sub.3                                                                          CH.sub.3                                             OCH.sub.3    H       CH.sub.3                                                                          OCH.sub.3                                            OC.sub.2 H.sub.5                                                                           H       OCH.sub.3                                                                         CH.sub.3                                             OCH(CH.sub.3).sub.2                                                                        H       OCH.sub.3                                                                         OCH.sub.3                                            OC(CH.sub.3).sub.3                                                                         H       OCH.sub.3                                                                         CH.sub.3                                             OCH(CH.sub. 3)C.sub.2 H.sub.5                                                              3-F     CH.sub.3                                                                          OCH.sub.3                                            OCH.sub.3    6-Br    OCH.sub.3                                                                         OCH.sub.3                                            Cl           H       CH.sub.3                                                                          CH.sub.3                                             Cl           H       CH.sub.3                                                                          OCH.sub.3                                            Cl           H       OCH.sub.3                                                                         CH.sub.3                                             Cl           H       OCH.sub.3                                                                         OCH.sub.3                                            Cl           6-CH.sub.3                                                                            CH.sub.3                                                                          C.sub.2 H.sub.5                                      Cl           H       OCH.sub.3                                                                         CH.sub.2 OC.sub.2 H.sub.5                            Cl           5-NO.sub.2                                                                            C.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                     Cl           H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                     Br           H       CH.sub.3                                                                          CH.sub.3                                             Br           H       OCH.sub.3                                                                         OCH.sub.3                                            F            H       OCH.sub.3                                                                         CH.sub.3                                             F            H       CH.sub.3                                                                          OCH.sub.3                                            CF.sub.3     H       CH.sub.3                                                                          CH.sub.3                                             CF.sub.3     H       OCH.sub.3                                                                         OCH.sub.3                                            CF.sub.3     H       OC.sub.2 H.sub.5                                                                  CH.sub.3                                             CF.sub.3     H       CH.sub.3                                                                          CF.sub.3                                             NO.sub.2     H       CH.sub.3                                                                          H                                                    NO.sub.2     H       CH.sub.3                                                                          OCH.sub.3                                            NO.sub.2     H       OCH.sub.3                                                                         CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                   NO.sub.2     6-Cl    OCH.sub.3                                                                         OCH.sub.3                                            NO.sub.2     H       OC.sub.2 H.sub.5                                                                  CH.sub.2 CH.sub.2 OCH.sub.3                          CO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH.sub. 3                                                                         H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          H                                                    CO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         O(CH.sub.2).sub.3 CH.sub.3                           CO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          OCH(CH.sub.3).sub.2                                  CO.sub.2 C.sub.2 H.sub.5                                                                   H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH(CH.sub.3).sub.2                                                                H       OC.sub.2 H.sub.5                                                                  OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                         H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                       H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 (CH.sub.2).sub.5 CH.sub.3                                                         H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 CH.sub.2 CHCH.sub.2                                                               H       CH.sub.3                                                                          Cl                                                   CO.sub.2 CH.sub.2 CHCH.sub.2                                                               H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.2 CHCHCH.sub.3                                                             H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.4 CHCH.sub.2                                                       H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH.sub.2 CF.sub.3                                                                 H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                              H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 (CH.sub.2).sub.3 Br                                                               H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.4 CHBrCH.sub.2 Br                                                  H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH(CF.sub.3)CH.sub.3                                                              H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.2 CCl.sub.3                                                                H       CH.sub.3                                                                          Cl                                                    ##STR23##   H       CH.sub.3                                                                          CH.sub.3                                              ##STR24##   H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                       H       CH.sub.3                                                                          H                                                    CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.2 CH.sub.3                                              H       CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 (CH.sub.2 CH.sub.2 O).sub.2 C.sub.2 H.sub.5                                       H       CH.sub.3                                                                          OCH.sub.3                                            CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                H       OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 (CH.sub.2).sub.3 OCH.sub.3                                                        H       OCH.sub.3                                                                         OCH.sub.3                                            CO.sub.2 (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                 H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 CH.sub.3                                                                          H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 CH.sub.3                                                                          H       OCH.sub.3                                                                         CH(CH.sub.3).sub.2                                   SO.sub.2 C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                      SO.sub.2 CH(CH.sub.3 ).sub.2                                                               H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                         H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                         H       OCH.sub.3                                                                         OCH.sub.3                                            SO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                       H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 OCH.sub.2 CF.sub.3                                                                H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 OCH.sub.2 CCl.sub.3                                                               H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 N(OCH.sub.3)CH.sub.3                                                              H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                     SO.sub.2 N(CH.sub.3).sub.2                                                                 H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 N(CH.sub.3).sub.2                                                                 H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                                 H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                        H       OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                   SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                          H       OCH.sub.3                                                                         OCH.sub.3                                            SO.sub.2 N(CH.sub.3)(CH.sub.2).sub.3 CH.sub.3                                              H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 N[CH(CH.sub.3).sub.2 ]CH.sub.3                                                    H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 N(CH.sub.3).sub.2                                                                 H       OCH.sub.3                                                                         (CH.sub.2).sub.3 CH.sub.3                            OCHF.sub.2   H       OCH.sub.3                                                                         OCH.sub.3                                            OCF.sub.3    H       CH.sub.3                                                                          CH.sub. 3                                            OCH.sub.2 CF.sub.3                                                                         H       CH.sub.3                                                                          CF.sub.3                                             OCF.sub.2 CHF.sub.2                                                                        H       CH.sub.3                                                                          Cl                                                   OCF.sub.2 CHFCl                                                                            H       CH.sub.3                                                                          OCH.sub.3                                            OCF.sub.2 CHFBr                                                                            H       OCH.sub.3                                                                         CH.sub.3                                             OCF.sub.2 CHFCF.sub.3                                                                      H       OC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.5                                     SO.sub.2 CHF.sub.2                                                                         H       CH.sub.3                                                                          CH.sub.3                                             SO.sub.2 CH.sub.2 CF.sub.3                                                                 H       CH.sub.3                                                                          OCH.sub.3                                            SO.sub.2 CF.sub.3                                                                          H       OCH.sub.3                                                                         CH.sub.3                                             SO.sub.2 CF.sub.2 CHF.sub.2                                                                H       OCH.sub.3                                                                         OCH.sub.3                                            SO.sub.2 CF.sub.2 CHFCF.sub.3                                                              H       CH.sub.3                                                                          CH.sub.3                                             OSO.sub.2 CH.sub.3                                                                         H       CH.sub.3                                                                          OCH.sub.3                                            OSO.sub.2 CH.sub.3                                                                         H       CH.sub.3                                                                          CH.sub.3                                             OSO.sub.2 C.sub.2 H.sub.5                                                                  H       CH.sub.3                                                                          OCH.sub.3                                            OSO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                        H       OCH.sub.3                                                                         CH.sub.3                                             OSO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                        H       OCH.sub.3                                                                         OCH.sub.3                                            OSO.sub.2 CH.sub.2 Cl.sub.2 Cl                                                             H       OCH.sub.3                                                                         CH.sub.3                                             OSO.sub.2 CF.sub.3                                                                         H       CH.sub.3                                                                          CH.sub.3                                             OSO.sub.2 CH.sub.2 CCl.sub.3                                                               H       OCH.sub.3                                                                         H                                                    OSO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Br                                                    H       OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 OCH.sub.3                                                                         H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 OC.sub.2 H.sub.5                                                                  H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.2 O(CH.sub.2).sub.2 CH.sub.3                                                        H       OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 OC(CH.sub.3).sub.3                                                                H       OCH.sub.3                                                                         OCH.sub.3                                            CH.sub.2 OCH(CH.sub.3).sub.2                                                               H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 OCH.sub.3                                                                         3-OCH.sub.3                                                                           OCH.sub.3                                                                         CH.sub.3                                             CH.sub.2 OCH.sub.3                                                                         H       CH.sub.3                                                                          OC.sub.2 H.sub.5                                     CH.sub.2 OCH.sub.2 CHCH.sub.2                                                              H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.2 OCH.sub.2 CHCHCH.sub.3                                                            H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 OCH.sub.2 C(CH.sub.3)CH.sub.2                                                     H       OCH.sub.3                                                                         OCH.sub.3                                            CH.sub.2 SO.sub.2 CH.sub.3                                                                 H       CH.sub.3                                                                          CH.sub.3                                             CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                        H       OCH.sub.3                                                                         OCH(CH.sub.3).sub.2                                  CH.sub.2 SO.sub.2 CH.sub.3                                                                 H       CH.sub.3                                                                          O(CH.sub.2).sub.3 CH.sub.3                           CH.sub.2 SO.sub.2 CH(CH.sub.3).sub.2                                                       H       OCH.sub.3                                                                         OCH.sub.3                                            CH.sub.2 SO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                H       CH.sub.3                                                                          OCH.sub.3                                            CH.sub.2 SO.sub.2 CH.sub.3                                                                 H       OC.sub.2 H.sub.5                                                                  CH.sub.3                                             CH.sub.2 SO.sub.2 (CH.sub.2 ).sub.2 CH.sub.3                                               H       C.sub.2 H.sub.5                                                                   OCH.sub.3                                            CH.sub.2 OC.sub.2 H.sub.5                                                                  5-OCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                             Cl           5-C.sub.2 H.sub.5                                                                     CH.sub.3                                                                          CH.sub.3                                             CH.sub.3     5-CH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                          OCH.sub.3                                            OCH.sub.3    5-(CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                                                          OCH.sub.3                                            Br           3-O(CH.sub.2).sub.2 CH.sub.3                                                          OCH.sub.3                                                                         OCH.sub.3                                            F            5-CF.sub.3                                                                            OCH.sub.3                                                                         CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          5-OC(CH.sub.3).sub.3                                                                  CH.sub.3                                                                          CH.sub.3                                             CO.sub.2 CH.sub.3                                                                          5-NO.sub.2                                                                            CH.sub.3                                                                          OCH.sub.3                                            __________________________________________________________________________

                  TABLE IIb                                                       ______________________________________                                         ##STR25##                                                                    R           R.sub.1                                                                              X       Y         m.p. (°C.)                        ______________________________________                                        Cl          H      OCH.sub.3                                                                             CH.sub.2 OC.sub.2 H.sub.5                          CF.sub.3    H      CH.sub.3                                                                              CF.sub.3                                           NO.sub.2    H      OCH.sub.3                                                                             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                 NO.sub.2    H      OC.sub.2 H.sub.5                                                                      CH.sub.2 CH.sub.2 OCH.sub.3                        CO.sub.2 CH.sub.3                                                                         H      OCH.sub.3                                                                             O(CH.sub.2).sub.3 CH.sub.3                         CO.sub.2 CH.sub.3                                                                         H      CH.sub.3                                                                              OCH(CH.sub.3).sub.2                                CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                      H      CH.sub.3                                                                              H                                                  SO.sub.2 CH.sub.3                                                                         H      OCH.sub.3                                                                             CH(CH.sub.3).sub.2                                 SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                       H      OCH.sub.3                                                                             CH.sub.2 OCH.sub.3                                 SO.sub.2 N(CH.sub.3).sub.2                                                                H      OCH.sub.3                                                                             (CH.sub.2).sub.3 CH.sub.3                          OCH.sub.2 CF.sub.3                                                                        H      CH.sub.3                                                                              CF.sub.3                                           OSO.sub.2 CH.sub.2 CCl.sub.3                                                              H      OCH.sub.3                                                                             H                                                  CH.sub.2 OCH.sub.3                                                                        H      OCH.sub.3                                                                             OC.sub.2 H.sub.5                                   CH.sub.2 SO.sub.2 CH.sub.3                                                                H      CH.sub.3                                                                              O(CH.sub.2).sub.2 CH.sub.3                         CO.sub.2 CH.sub.3                                                                         H      CH.sub.3                                                                              H                                                  ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid inertdiluent(s). More specifically, they will contain these ingredients inthe following approximate proportions:

                  TABLE III                                                       ______________________________________                                                          Weight Percent*                                                         Active  Inert                                                                 Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a surfactant or an inert diluent      equals 100 weight percent.                                               

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid inert diluents are described in Watkins, et al., "Handbookof Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, New Jersey, but other solids, either mined or manufactured,may be used. The more absorptive diluents are preferred for wettablepowders and the denser ones for dusts. Typical liquid inert diluents andsolvents are described in Marsden, "Solvents Guide," 2nd Ed.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutcheon's Detergents andEmulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as wellas Sisely and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc., New York, 1964, list surfactants and recommendeduses. All formulations can contain minor amounts of additives to reducefoaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions, i.e., formulations, are wellknown. Solutions are prepared by simply mixing the ingredients. Finesolid compositions are made by blending and, usually, grinding as in ahammer or fluid energy mill. Suspensions are prepared by wet milling(see, for example, Littler, U.S. Pat. No. 3,060,084). Granules andpellets can be made by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See J. E. Browning,"Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and"Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York,1973, pp. 8-57ff.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 11 Wettable Powder

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            80%                                               sodium alkylnaphthalenesulfonate                                                                           2%                                               sodium ligninsulfonate       2%                                               synthetic amorphous silica   3%                                               kaolinite                   13%                                               ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 12 Wettable Powder

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            50%                                               sodium alkylnaphthalenesulfonate                                                                           2%                                               low viscosity methyl cellulose                                                                             2%                                               diatomaceous earth          46%                                               ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 13 Granule

    ______________________________________                                        Wettable Powder of Example 10                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 14 Extruded Pellet

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            25%                                               anhydrous sodium sulfate    10%                                               crude calcium ligninsulfonate                                                                              5%                                               sodium alkylnaphthalenesulfonate                                                                           1%                                               calcium/magnesium bentonite 59%                                               ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 15 Oil Suspension

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            25%                                               polyoxyethylene sorbitol hexaoleate                                                                        5%                                               highly aliphatic hydrocarbon oil                                                                          70%                                               ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 16 Wettable Powder

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            20%                                               sodium alkylnaphthalenesulfonate                                                                           4%                                               sodium ligninsulfonate       4%                                               low viscosity methyl cellulose                                                                             3%                                               attapulgite                 69%                                               ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles substantially all below about 100 microns, thematerial is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mmopening) and packaged.

EXAMPLE 17 Low Strength Granule

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                             1%                                               chlorobenzene                9%                                               attapulgite granules        90%                                               (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 18 Aqueous Suspension

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            40%                                               polyacrylic acid thickener  0.3%                                              dodecylphenol polyethylene glycol ether                                                                   0.5%                                              disodium phosphate          1%                                                monosodium phosphate        0.5%                                              polyvinyl alcohol           1.0%                                              water                       56.7%                                             ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 19 Low Strength Granule

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            0.1%                                              attapulgite granules        99.9%                                             (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 20 Emulsifiable Concentrate

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            30%                                               blend of oil soluble sulfonates and                                           polyoxyethylene ethers       4%                                               chlorobenzene               66%                                               ______________________________________                                    

The ingredients are combined and stirred with gentle warming to speedsolution. A fine screen filter is included in packaging operation toinsure the absence of any extraneous undissolved material in theproduct.

EXAMPLE 21 Granule

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            80%                                               wetting agent                1%                                               crude ligninsulfonate salt (containing                                                                    10%                                               5-20% of the natural sugars)                                                  attapulgite clay             9%                                               ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 22 High Strength Concentrate

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                             99%                                              silica aerogel              0.5%                                              synthetic amorphous silica  0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 23 Wettable Powder

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                             90%                                              dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 24 Wettable Powder

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            40%                                               sodium ligninsulfonate      20%                                               montmorillonite clay        40%                                               ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 25 Oil Suspension

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            35%                                               blend of polyalcohol carboxylic                                                                            6%                                               esters and oil soluble petroleum                                              sulfonates                                                                    xylene                      59%                                               ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 26 Dust

    ______________________________________                                        2-Chloro-N--(5,7-dimethyl-2H--[1,2,4]oxadiazolo-                              [2,3-a]-pyrimidin-2-ylidene)benzenesulfonamide                                                            10%                                               attapulgite                 10%                                               pyrophyllite                80%                                               ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

Utility

The compounds of the present invention are active herbicides. They haveutility for broad-spectrum pre- and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,oil-well sites, drive-in theaters, around billboards, highway andrailroad structures.

The precise amount of the compounds of Formula I to be used in any givensituation will vary according to the particular end result desired, theamount of foliage present, the weeds to be controlled, the soil type,the formulation and mode of application, weather conditions, etc. Sinceso many variables play a role, it is not possible to state a rate ofapplication suitable for all situations. Broadly speaking, the compoundsof this invention are used at levels of about 0.01 to 20 kg/ha with apreferred range of 0.1 to 10 kg/ha. The higher rates of application fromwithin this range will normally be selected for adverse conditions orwhere extended persistence in soil is desired.

The compounds of Formula I may be used in combination with any othercommercial herbicide such as the triazine, triazole, uracil, urea,amide, diphenylether, carbamate and bipyridylium types.

The activity of these compounds was discovered in greenhouse tests. Thetests are described and the data resulting from them are shown below.

Test A

Seeds of crabgrass (Digitaria spp.), barnywardgrass (Echinochloacrusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia),morningglory (Ipomoea spp.), cocklebur (Xanthium spp.), sorghum, corn,soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were plantedin a growth medium and treated pre-emergence with the chemicalsdissolved in a non-phytotoxic solvent solution of the compounds of TableA. At the same time, cotton having five leaves (including cotyledonaryones), bush beans with the third trifoliolate leaf expanding, crabgrass,barnyardgrass and wild oats with two leaves, sicklepod with three leaves(including cotyledonary ones), morningglory and cocklebur with fourleaves (including the cotyledonary ones), sorghum and corn with fourleaves, soybean with two cotyledonary leaves, rice with three leaves,wheat with one leaf, and nutsedge with three-five leaves were sprayedwith a non-phytotoxic solvent solution of the compounds of Table A.Other containers of the above untreated weeds and crops were treatedpre- or post-emergence with the same non-phytotoxic solvent so as toprovide a solvent control. A set of untreated control plants was alsoincluded for comparison. Pre-emergence and post-emergence treated plantsand controls were maintained in a greenhouse for sixteen days, then alltreated plants were compared with their respective controls and ratedvisually for response to treatment.

The following rating system was used:

O=no effect

10=maximum effect

C=chlorosis or necrosis

D=defoliation

E=emergence inhibition

G=growth retardation

H=formative effects

6Y=abscised buds or flowers

U=unusual pigmentation and

X=axillary stimulation.

    ______________________________________                                        Compounds                                                                     ______________________________________                                        Compound 1                                                                              ##STR26##                                                           Compound 2                                                                              ##STR27##                                                           Compound 3                                                                              ##STR28##                                                           Compound 4                                                                              ##STR29##                                                           Compound 5                                                                              ##STR30##                                                           Compound 6                                                                              ##STR31##                                                           ______________________________________                                    

                                      TABLE A                                     __________________________________________________________________________            Cmpd. 1                                                                             Cmpd. 2                                                                            Cmpd. 2                                                                            Cmpd. 3                                                                             Cmpd. 4                                                                            Cmpd. 5                                                                             Cmpd. 6                                                                            Cmpd. 6                         Rate kg/ha                                                                            0.4   0.4  0.05 0.4   0.4  0.4   0.4  0.05                            __________________________________________________________________________    Post-emergence                                                                Bushbean                                                                              10D,9G,6Y                                                                           9C   9C   9D,9G,6Y                                                                            9C   8D,9G,6Y                                                                            9C,  9C                              Cotton  3U,3C,9G                                                                            5C,9G                                                                              4C,9G                                                                              3C,8G 5C,9G                                                                              5C,9G 4C,8G                                                                              5C,9G                           Morningglory                                                                          9C    9C   9C   10C   9C   10C   9C   9C                              Cocklebur                                                                             9C    9C   1C,7H                                                                              5G    6C,9G                                                                              9C    9C   9C                              Cassia  5C,9G 9C   6C,9G                                                                              2C,7H 9C   9C    6C,9G                                                                              9C                              Nutsedge                                                                              6C,9G 5C,9G                                                                              5G   1C,7G 6C,9G                                                                              6C,9G 6C,9G                                                                              8G,2C                           Crabgrass                                                                             1C,8G 6C,9G                                                                              4C,9G                                                                              2C,5G 6C,9G                                                                              4C,8G 9C   4C,9G                           Barnyardgrass                                                                         6C,9G 10C  6C,9H                                                                              5C,9H 9C   10C   10C  10C                             Wild Oats                                                                             3C,9G 6C,9H                                                                              2C,6G                                                                              8G,5X 4C,9G                                                                              3C,9G 5C,9G                                                                              3C,9G                           Wheat   2C,9G 3C,9G                                                                              3C,9G                                                                              8G,5X 4C,9G                                                                              2C,9G 5C,9G                                                                              3C,9G                           Corn    6U,9G 3U,9G                                                                              4C,9H                                                                              6U,9G 10C  10C   5C,9G                                                                              4C,9G                           Soybean 5C,9G 9C   6C,9G                                                                              10C   9C   9C    9C   9C                              Rice    6C,9G 5C,9G                                                                              5C,9G                                                                              6C,9G 6C,9G                                                                              6C,9G 6C,9G                                                                              6C,9G                           Sorghum 10C   4C,9G                                                                              3C,9G                                                                              2C,9G 9C   5C,9G 9C   9C                              Pre-emergence                                                                 Morningglory                                                                          9G    9C   3C,9G                                                                              3C,9G 9H   9C    9C   4C,9G                           Cocklebur                                                                             3C,9H 9H,6C                                                                              9H,3C                                                                              2C    9H   9H    9H   9H                              Cassia  3C,9G 9C   6C,9G                                                                              3C,7G 8H,5C                                                                              3C,9G 9C   5C,9G                           Nutsedge                                                                              3C,9G 5C,8G                                                                              2C,7G                                                                              2C    3C,9G                                                                              2C,5G 5C,9G                                                                              3C,7G                           Crabgrass                                                                             3C,8G 6C,9G                                                                              3C,8H                                                                              2C,8G 3C,8G                                                                              5C,8G 6C,9G                                                                              4C,7G                           Barnyardgrass                                                                         3C,9H 6C,9H                                                                              4C,9H                                                                              5C,9H 9H   5C,9H 6C,9H                                                                              5C,9H                           Wild Oats                                                                             2C,8G 6C,9G                                                                              5C,9G                                                                              2C,8G 3C,9H                                                                              4C,8G 5C,9G                                                                              3C,9G                           Wheat   8G    6C,9G                                                                              3C,8G                                                                              1C,7G 2C,9H                                                                              3C,9G 3C,9G                                                                              3C,9G                           Corn    9G    6C,9H                                                                              3C,9H                                                                              3C,9H 2C,9H                                                                              3C,9G 2C,9G                                                                              3C,9G                           Soybean 2C,6H 5C,8H                                                                              4C,8H                                                                              2C,6H 2C,8H                                                                              4C,7H 5C,8H                                                                              4C,7H                           Rice    10E   5C,9H                                                                              5C,9H                                                                              9H    10E  10E   10E  5C,9H                           Sorghum 6C,9H 6C,9H                                                                              5C,9G                                                                              5C,9H 2C,9H                                                                              5C,9H 5C,9H                                                                              5C,9H                           __________________________________________________________________________

Test B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonslit loam soil. One pan was planted with corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted withcotton, soybeans, purple nutsedge (Cyperus rotundus), and severalbroadleaf weeds. The following grassy and broadleaf weeds were planted:crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pensylvanicum), pigweed (Amaranthus retroflexus), morningglory(Ipomoea hederacea), sicklepod (Cassia obtusifolia), teaweed (Sidaspinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Daturastramonium). A 12.5 cm diameter plastic pot was also filled withprepared soil and planted with rice and wheat. Another 12.5 cm pot wasplanted with sugarbeets. The above four containers were treatedpreemergence with several test compounds within the scope of theinvention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B.

                  TABLE B                                                         ______________________________________                                        PRE-EMERGENCE ON FALLSINGTON SILT LOAM SOIL                                    ##STR32##                                                                                   kg/ha                                                          Pre-Emergence    0.25        0.06                                             ______________________________________                                        Rice             6G,7E       6G                                               Barnyardgrass    4G,2C       0                                                Wheat            3G          0                                                Wild Oats        0           0                                                Crabgrass        0           0                                                Sorghum          8G,5H       4G,3H                                            Johnsongrass     5G,3H       2G                                               Dallasgrass      4G          3G                                               Giant Foxtail    3G          3G                                               Bluegrass        3G          0                                                Cheatgrass       4G          0                                                Corn             3G          0                                                Mustard          8G,8C       0                                                Cocklebur        --          0                                                Pigweed          7G          0                                                Nutsedge         3G          0                                                Cotton           2G          0                                                Morningglory     0           0                                                Cassia           2G          0                                                Teaweed          0           0                                                Velvetleaf       0           0                                                Jimsonweed       0           0                                                Soybean          0           0                                                Sugarbeet        4G          2G                                               ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR33## where R isC₁ -C₄ alkyl, C₁ -C₄ alkoxy, F, Cl, Br, NO₂, COR₄, SO₂ R₅, SO₂ NR₆ R₇,SO₂ OCH₂ CF₃, SO₂ OCH₂ CCl₃, SO₂ N(OCH₃)(CH₃), BR₈, OSO₂ R₉ or CH₂ P;R₁is H, F, Cl, Br, CF₃, NO₂, C₁ -C₄ alkyl or C₁ -C₄ alkoxy; R₄ is C₁ -C₆alkoxy, C₃ -C₆ alkenyloxy, C₂ -C₆ haloalkoxy substituted with 1-3 atomsselected from F, Cl, or Br, C₅ -C₆ cycloalkoxy, --O(CH₂ CH₂ O)_(n) R₁₀or OCH₂ CH₂ CH₂ OR₁₀ ; n is 1 or 2; R₅ is C₁ -C₄ alkyl; R₆ and R₇ areindependently C₁ -C₄ alkyl, provided the total number of carbon atoms ofR₆ and R₇ does not exceed 5; B is O or SO₂ ; R₈ is CHF₂, CF₃, CH₂ CF₃,CF₂ CHFG where G is F, Cl, Br or CF₃ ; R₉ is C₁ -C₄ alkyl or C₁ -C₄alkyl substituted with 1-3 atoms selected from F, Cl or Br; P is C₁ -C₄alkoxy, C₃ -C₄ alkenyloxy or SO₂ R₅ ; R₁₀ is CH₃ or CH₃ CH₂ ; X is CH₃,CH₃ CH₂, CH₃ O or CH₃ CH₂ O; Y is H, Cl, CF₃, C₁ -C₄ alkyl, C₁ -C₄alkoxy, CH₂ OCH₃, CH₂ OCH₂ CH₃, CH₂ CH₂ OCH₃ or CH₂ CH₂ OCH₂ CH₃ ; and Zis CH and their agriculturally suitable salts.
 2. A compound of claim 1wherein R is C₁ -C₄ alkyl, C₁ -C₄ alkoxy, F, Cl, Br, CF₃, SO₂ R₅, BR₈,OSO₂ R₉ or CH₂ P, where P is C₁ -C₄ alkoxy and R₁ is H, F, Cl, Br, CF₃,C₁ -C₄ alkyl or C₁ -C₄ alkoxy.
 3. A compound of claim 2 wherein R₁ is H.4. A compound of claim 3 wherein R is C₁ -C₃ alkyl, C₁ -C₃ alkoxy, F,Cl, Br, CF₃, SO₂ R₅, BR₈, OSO₂ R₉ or CH₂ P; provided that:(a) when R isSO₂ R₅, then R₅ is C₁ -C₃ alkyl; (b) when R is BR₈, then BR₈ is SO₂ CF₃or OCF₂ CF₂ H; (c) when R is OSO₂ R₉, then R₉ is C₁ -C₃ alkyl or CF₃ ;and (d) when R is CH₂ P, then P is CH₃ O.
 5. A compound of claim 4wherein Y is H, CF₃, C₁ -C₂ alkyl, C₁ -C₂ alkoxy or CH₂ OCH₃.
 6. Acompound of claim 5 wherein X is CH₃ or CH₃ O and Y is CH₃ or CH₃ O. 7.The compound of claim 1,2-Chloro-N-(5,7-dimethyl-2H-[1,2,4]oxadiazolo[2,3-a]pyrimidin-2-yl-idene)benzenesulfonamide.
 8. The compound of claim 1,2-Chloro-N-(5-methoxy-7-methyl-2H-[1,2,4]oxadiazolo[2,3-a]pyrimidin-2-ylidene)benzenesulfonamide.9. The compound of claim 1,N',N'-dimethyl-N-(5,7-dimethyl-2H-1,2,4-oxadiazolo[2,3-A]pyrimidin-2-yl)-1,2-benzenedisulfonamide.10. The compound of claim 1,N',N'-dimethyl-N-(5-methoxy-7-methyl-2H-1,2,4-oxadiazolo[2,3-A]pyrimidin-2-yl)-1,2-benzenedisulfonamide.11. A compound of the formula: ##STR34## wherein X is CH₃, CH₃ CH₂, CH₃O or CH₃ CH₂ O;Y is H, Cl, CF₃, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, CH₂ OCH₃,CH₂ OCH₂ CH₃, CH₂ CH₂ OCH₃ or CH₂ CH₂ OCH₂ CH₃ ; and Z is CH.
 12. Thecompound of claim 11 wherein Y is H, CF₃, C₁ -C₂ alkyl, C₁ -C₂ alkoxy orCH₂ OCH₃.
 13. The compound of claim 12 wherein X is CH₃ or CH₃ O, and Yis CH₃ or CH₃ O.
 14. A composition suitable for controlling the growthof undesired vegetation consisting essentially of an effective amount ofa compound of claim 1 and at least one of a surfactant and a solid orliquid inert diluent.
 15. A composition suitable for controlling thegrowth of undesired vegetation consisting essentially of an effectiveamount of a compound of claim 2 and at least one of a surfactant and asolid or liquid inert diluent.
 16. A composition suitable forcontrolling the growth of undesired vegetation consisting essentially ofan effective amount of a compound of claim 3 and at least one of asurfactant and a solid or liquid inert diluent.
 17. A compositionsuitable for controlling the growth of undesired vegetation consistingessentially of an effective amount of a compound of claim 4 and at leastone of a surfactant and a solid or liquid inert diluent.
 18. Acomposition suitable for controlling the growth of undesired vegetationconsisting essentially of an effective amount of a compound of claim 5and at least one of a surfactant and a solid or liquid inert diluent.19. A composition suitable for controlling the growth of undesiredvegetation consisting essentially of an effective amount of a compoundof claim 6 and at least one of a surfactant and a solid or liquid inertdiluent.
 20. A composition suitable for controlling the growth ofundesired vegetation consisting essentially of an effective amount ofthe compound of claim 7 and at least one of a surfactant and a solid orliquid inert diluent.
 21. A composition suitable for controlling thegrowth of undesired vegetation consisting essentially of an effectiveamount of the compound of claim 8 and at least one of a surfactant and asolid or liquid inert diluent.
 22. A composition suitable forcontrolling the growth of undesired vegetation consisting essentially ofan effective amount of the compound of claim 9 and at least one of asurfactant and a solid or liquid inert diluent.
 23. A compositionsuitable for controlling the growth of undesired vegetation consistingessentially of an effective amount of the compound of claim 10 and atleast one of a surfactant and a solid or liquid inert diluent.
 24. Amethod for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 1. 25. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 2. 26. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim3.
 27. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 4. 28. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 5. 29. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim6.
 30. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount ofthe compound of claim
 7. 31. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of the compound of claim
 8. 32. A methodfor controlling the growth of undesired vegetation which comprisesapplying to the locus to be protected an effective amount of thecompound of claim
 9. 33. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of the compound of claim 10.